ES2536627T3 - Compositions comprising an active substance and a graft polymer of vinyl ester and poly (alkylene oxide) - Google Patents

Abstract

A composition comprising: an active substance; and a polymeric additive, which is obtained by graft polymerization, comprising: ** Formula ** 1) at least one unit represented by formula (I): ** Formula ** in which each R is independently selected from the group of a hydrogen atom, an alkyl group, an aryl group, and combinations thereof; and Z comprises at least units represented by formula (II): wherein each R1 is independently selected from the group of a hydrogen atom, an alkyl group, an aryl group, a carbonyl group, a hydroxyl group, an ether group, and their combinations; and R2 is a C1-C10 hydrocarbon group; and 2) at least one unit represented by formula (III): ** Formula ** in which A is an alkyleneoxy group having 2 to 10 carbon atoms.

Description

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DESCRIPTION

Compositions comprising an active substance and a graft polymer of vinyl ester and poly (alkylene oxide)

The present invention relates, in general, to a composition comprising an active substance and a polymeric additive. More specifically, the present invention relates to a composition comprising a polymeric additive that is capable of increasing the performance and / or stability of the acitva substance in the composition.

Compositions comprising an active substance are useful for many applications. A specific example of a useful composition is an agrochemical composition comprising an active pesticide ingredient as the active substance. In some cases, the agrochemical compositions are prepared by diluting the active pesticide ingredient with water, the agrochemical compositions being applied to plants to thus administer the active pesticide ingredient.

The performance and stability of the compositions comprising the active substance in general is a cause for concern, especially for compositions that include pesticide active ingredients. In addition, conservation and temperature cycles before application generally exacerbate the stability problems of the active substances in the compositions, and there is a constant desire to improve stability during storage and after freezing / thawing of substances active in said compositions to avoid separation between the active substances and the compositions.

The problems with the stability of the active substances can be attributed to the fact that many active substances are capable of maturing Ostwald. Ostwald maturation is a phenomenon that leads to the instability of some active substances in compositions. Although many active substances do not show maturation of Ostwald, it can be produced under some circumstances when the compositions contain a continuous aqueous phase and an active substance that is capable of being transported through the continuous aqueous phase. In general, Ostwald maturation occurs through a mechanism in which smaller particles are incorporated into larger particles because larger particles are more energetically favored than smaller particles. The growth of the particle size due to the maturation of Ostwald usually leads to instability of the active substance in the compositions, because larger particles in general are more likely to decant from the compositions.

The maturation of Ostwald in general is facilitated by the dissolution of the active substances in the continuous aqueous phase, which occurs even if the solubility of the active substances in the water is low. However, the high solubility of active substances in water increases the appearance of Ostwald maturation for active substances that are capable of Ostwald maturation. For this reason, and because many pesticide active ingredients are capable of maturing with Ostwald, many water-based agrochemical compositions employ pesticide active ingredients that have a relatively low water solubility of less than 100 ppm in water.

The use of various additives to enhance the stability of the compositions is known, including compositions that include active substances capable of undergoing Ostwald maturation. Examples of these additives include poloxamers and industry models, such as Morwet® D425 and the recently developed Atlox® 4913. Morwet® D425 is a sulphonate condensate of naphthaleneformaldehyde, and Atlox® 4913 is a grafted polymer comprising a skeleton of methyl methacrylate and methacrylic acid units and polyethylene glycol side chains with a methoxy group cap. While Atlox® 4913 is widely used, further attempts are made to develop new additives that act as well or better than Atlox® 4913 to increase the performance and / or increase the stability of the active substances included in the compositions. Improvements in the inhibition of Ostwald maturation by means of new additives may lead to the ability to use active substances that are more water soluble in the compositions, while still allowing sufficient stability of the active substances included in the compositions.

In addition to a high stability of the compositions comprising the active substance, a high performance of the active substance in general is also a cause for concern, especially for compositions that include pesticide active ingredients. In general, high stability, as well as high performance, should be achieved at the same time.

WO 2005/036963 describes a suspension concentrate comprising a marketed azol and / or strobilurin, a penetration enhancer, a dispersant and water. The dispersant can be a polymer of the methyl ester of 2-methyl-2-propenoic acid and α- (2-methyl-1-oxo-2-propenyl) -ω-methoxy-poly (oxy-1,2-ethanediyl).

Liang et al. (Langmuir, 2000, 16, 1306-1310) analyze dispersion stability in the presence of grafted copolymers.

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Haas et al. (Colloids Surfaces, A, 2001, 183-185, 785-793) analyze the influence of polymeric surfactants on pesticide suspension concentrates with respect to dispersant capacity, grinding efficiency and stabilization power.

Summary of the invention and advantages

The present invention provides a composition and method for preparing the composition. The composition comprises an active substance and a polymeric additive. The polymeric additive comprises:

1) at least one unit represented by formula (I):

image 1

wherein each R is independently selected from the group of a hydrogen atom, an alkyl group, an aryl group, and combinations thereof; and Z comprises at least 10 units represented by formula (II):

wherein A is an alkyleneoxy group having 2 to 10 carbon atoms.

The process for preparing the composition comprises the step of combining the active substance and the polymeric additive to form the composition.

The composition of the present invention shows excellent performance and stability. In fact, the performance and stability of the composition is comparable to the performance and stability achieved when using Morwet® D425 or Atlox® 4913 model additives, achieving superior results under certain circumstances.

Detailed description of the invention

A composition and method for preparing the composition is provided. The composition comprises an active substance and a polymeric additive.

The active substance generally includes, but is not limited to biologically active substances, that is, substances that have an adverse or beneficial effect on living matter. As described in more detail below, the active substance may also include any substance capable of being transported through a continuous aqueous phase to thereby produce Ostwald maturation. However, it should be appreciated that the active substance is not limited to substances that are biologically active or to substances capable of being transported through a continuous aqueous phase. The active substance may be in liquid or solid particle form. In addition, the active substance may be water soluble, water insoluble, partially water soluble, fat soluble, lipo insoluble, and combinations thereof. An example of an active substance that is partially water soluble includes, but is not limited to an active substance that has a low water solubility of up to 500 ppm at temperatures from -15 ° C to 54 ° C. It should be appreciated that the composition may include a combination of active substances that are in general as described above. In one embodiment, the active substance may comprise solid particles of a partially water-soluble pesticide active ingredient. In another embodiment, the active substance may comprise an active ingredient of liquid pesticide that is fat-soluble and water-soluble. In embodiments in which the active substance comprises an active pesticide ingredient, the composition can be used to treat plants by applying the composition to the plants. In another embodiment, the present invention relates to a method for controlling phytopathogenic fungi and / or unwanted plant growth and / or an unwanted attack of insects or mites and / or for regulating plant growth, in which the Composition according to the invention is allowed to act on the specific pest, its habitat or the plants to be protected against the specific pest, the soil and / or on unwanted plants and / or useful plants and / or their habitat.

In a preferred embodiment, the active substance is an active pesticide ingredient (also called a pesticide). The term pesticide refers to at least one pesticide selected from the group of fungicides, insecticides, nematicides, herbicides, pesticide antidotes and / or growth regulators. Preferred pesticides are fungicides, insecticides, herbicides and growth regulators. Pesticides especially

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Preferred are fungicides. Mixtures of pesticides of two or more of the aforementioned classes may also be used. Those skilled in the art are familiar with these pesticides, which can be found, for example, in the Pesticide Manual, 14th ed. (2006), The British Crop Protection Council, London. Examples of suitable pesticides are:

A) Strobilurins

-azoxiestrobina, cumetoxiestrobina, cumoxiestrobina, dimoxystrobin, enestroburin, fluoxaestrobin, kresoximometilo, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pirametoestrobina, piraoxiestrobina, pyribencarb, trifloxystrobin, methyl 2- [2- (2,5-dimethylphenoxymethyl) phenyl] - 3-methoxyacrylic and 2- (2- (3- (2,6-dichlorophenyl) -1-methylalkylidenaminooxymethyl) phenyl) -2-methoxyimino-N-methylacetamide;

B) Carboxamides

-carboxanilidas: benalaxyl, benalaxyl-M, benodanil, Bixafen, boscalid, carboxin, fenfuramo, fenhexamid, flutolanil, fluxapyroxad, furametpiro, isopirazamo, isotianilo, kiralaxilo, mepronil, metalaxyl, metalaxyl-M (mefenoxamo), ofurace, oxadixyl, oxycarboxin, penfluphene, pentiopirad, sedaxane, tecloftalamus, tifluzamide, thiadinyl, 2-amino-4-metolthiazol-5-carboxanilide, N- (4'-trifluoromethylthiobiphenyl-2-yl) -3-difluoromethyl-1-methyl-4H-pyrazide and N- (2- (1,3,3-trimethylbutyl) phenyl) -1,3-dimethyl-5-fluoro-1 H -pyrazol-4-carboxamide;

carboxylic morpholides: dimetomorf, flumorf, pyrimorf;

-amides of benzoic acid: flumetover, fluopicolide, fluopyramus, zoxamide;

-other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracycline, siltofamo and N- (6-methoxypyridin-3-yl) cyclopropancarboxylic acid amide;

C) Azoles

-triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazol, penconazole, propiconazole, prothioconazole, simeconazole , tebuconazole, tetraconazole, triadimephon, triadimenol, triticonazole, uniconazole;

-imidazoles: ciazofamid, imazalil, pefurazoate, prochloraz, triflumizol;

-benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;

-other: etaboxamo, etridiazol, himexazol and 2- (4-chlorophenyl) -N- [4- (3,4-dimethoxyphenyl) isoxazol-5-yl] -2-prop-2-yloxyacetamide;

D) Heterocyclic compounds

-pyridines: fluazinamo, pyrifenox, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine, 3- [5- (4-methylphenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine ;

-pyrimidines: bupirimate, ciprodinyl, diflumetoryme, fenarimol, ferimzone, mepanipyrimous, nitrapirine, nuarimol, pyrimethanil;

-piperazines: triforin;

-propyls: fenpiclonil, fludioxonil;

-morpholines: aldimorf, dodemorf, dodemorf-acetate, fenpropimorf, tridemorf;

-piperidines: fenpropidin;

-dicarboximides: fluoroimid, iprodione, procimidone, vinclozolin;

- 5-aromatic non-aromatic heterocycles: famoxadone, phenamidone, flutianyl, octylinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihdropyrazol-1-carbothioic acid Salicylic ester;

-other: acibenzolar-S-methyl, ametoctradine, amisulbrom, anilazine, blasticidin-S, captafol, captane, quinomethionate, dazomet, debacarb, dichlomezine, diphezoquat, diphezoquatmethylsulfate, phenoxyanil, folpet, oxyquinoline, pipeline, pyrinoxyquinone, pipeline triazoxide, triciclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5-chloro-1- (4,6-dimethoxypyrimidin-2-yl) -2-methyl-1H-benzoimidazole and 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) [1,2,4] triazolo [1,5-a] pyrimidine;

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E) Carbamates

-thio-and dithiocarbamates: ferbamo, mancozeb, maneb, metamo, metasulphocarb, metiramo, propineb, tiramo, zineb, ziramo;

-carbamates: bentiavalicarb, dietofencarb, iprovalicarb, propamocarb, propamocarb hydrochloride, valifenalate and N- (1- (1- (1- (4-cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid ester;

F) Other active substances

-guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadintriacetate, iminoctadine-tris (albesylate);

-antibiotics: kasugamycin, kasugamycin hydrochloride, streptomycin, polyoxin, validamycin A;

- nitrophenyl derivatives: binapacryl, dichloro, dinobutone, dinocap, nitrotal-isopropyl, tecnazeno;

-organic compounds. Phentine salts, such as phentine acetate, phentine chloride or phentine hydroxide;

- sulfur-containing heterocyclic compounds: dithianone, isoprotiolane;

-organophosphorus compounds: ediphenphos, phosethyl, phosphoryl aluminum, iprobenphos, phosphorous acids and their salts, pyrazophos, tolclofos-methyl;

-organochlorine compounds: chlorothalonyl, diclofluanid, dichlorophene, flusulfamide, hexachlorobenzene, pencicurone, pentachlorophenol and its salts, phthalamide, fifthzene, thiophanate-methyl, tolylfluanide, N- (4-chloro-2-nitrophenyl-phenyl) -ammonium;

-organic active substances: mixture of Bordeaux, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

- antifungal biocontrol agents, plant bioactivators: Ampelomyces quisqualis (for example, AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (for example, AFLAGUARD® from Syngenta, CH), Aureobasidium pullulans (for example, BOTECTOR® from bio-ferm GmbH, Germany), Bacillus pumilius (for example, isolated NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from Fa. AgraQuest Inc., USA), Bacillus subtilis var. amyloliquefaciens FZB24 (for example, TAEGRO® from Novozyme Biologicals, Inc., USA), Candida oleophila I-82 (for example, ASPIRE® from Ecogen Inc., USA), Candida saitoana (for example, BIOCURE® (mixed with lysozyme ) and BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta), chitosan (for example, ARMOR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f. catenulata, also called Gliocladium catenulatum (for example, isolated J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (for example, CONTANS® from Prophyta, Germany), Cryphonectria parasitica (for example, CNICM parasitic endothia, France), Cryptococcus albidus (for example, YIELD PLUS® from Anchor Bio-Technologies, South Africa), Fusarium oxysporum (for example, BIOFOX® from SIAPA, Italy, FUSACLEAN® from Natural Plant Protection, France), Metschnikowia fructicola (for example, SHEMER® from Agrogreen , Israel), Microdochium dimerum (e.g., ANTIBOT® from Agrauxine, France), Phlebiopsis gigantea (e.g., ROTSOP® from Verdera, Finland), Pseudozyma flocculosa (e.g., SPORODEX® from Plant Products Co. Ltd., Canada) , Pythium oligandrum DV74 (for example, POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Republic), Reynoutria sachlinensis (for example, REGALIA® from Marrone BioInnovations, USA), Talaromyces flavus V117b (for example, PROTUS® from Pro phyta, Germany), Trichoderma asperellum SKT-1 (for example, ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride LC52 (for example, SENTINEL® from Agrimm Technologies Ltd, NZ), T Harzianum T22 (for example, PLANTSHIELD® from Signature BioWorks Inc., USA), T. harzianum TH 35 (for example, ROOT PRO® from Mycontrol Ltd., Israel), T. harzianum T-39 (for example, TRICHODEX® and TRICHODERMA 2000® from Mycontrol Ltd., Israel, and Makhteshim Ltd., Israel), T. harzianum and T. viride (e.g., TRICHOPEL from Agrimm Technologies Ltd., NZ), T. harzianum ICC012 and T. viride ICC080 ( for example, REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T. harzianum (for example, BINAB® from BINAB Bio-Innovation AB, Sweden), T. stromaticum (for example, TRICOVAB® from CEPLAC, Brazil) , T. virens GL-21 (for example, SOILGARD® from Certis LLC, USA),

T. viride (for example, TRIECO® from Ecosense Labs. (India) Pvt. Ltd., India, BIO-CURE® F from T. Stanes & Co. Ltd., India), T. viride TV1 (for example, T Virid TV1 from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (for example, BOTRY-ZEN® from Botry-Zen Ltd., NZ);

-other: biphenyl, bronopol, ciflufenamide, cimoxanilp, diphenylamine, metrafenone, pyrophene, mildiomycin, oxinacobre, prohexadione-calcium, spiroxamine, tebufloquine, tolylfluanid, N- (cyclopropylmethioxyimino- (6-difluoromethyl) -2 phenylacetamide, N '- (4- (4-chloro-3-trifluoromethylphenoxy) -2,5-dimethylphenyl) -N-ethyl-N-methylformamidine, N' - (4- (4-fluoro-3-trifluoromethylphenoxy) -2 , 5-dimethylphenyl) -N-ethyl-N-methylformamidine, N '- (2-methyl-5-trifluoromethyl-4- (3

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trimethylsilanylpropoxy) phenyl) -N-ethyl-N-methylformamidine, N '- (5-difluoromethyl-2-methyl-4- (3-trimethylsilanylpropoxy) phenyl) -N-ethylN-methylformamidine, methyl- (1,2,3, 2- {1- [2- (5-Methyl-3-trifluoromethylpyrazol-1-yl) acetyl] piperidin-4-yl} thiazole-4-carboxylic acid, methyl- (R-4-tetrahydro-naphthalen-1-yl) amide ) 2- {1- [2- (5-Methyl-3-trifluoromethylpyrazol-1-yl) acetyl] piperidin-4-yl} thiazol-4- acid -1,2,3,4-tetrahydro-naphthalen-1-ylamide carboxylic acid, 6-tert-butyl-8-fluoro-2,3-dimethylquinolin-4-yl ester of methoxyacetic acid and N-methyl-2- {1 - [(5-methyl-3-trifluoromethyl-1H-pyrazole-1 -yl) acetyl] piperidin-4-yl} -N - [(1R) -1,2,3,4-tetrahydro-naphthalen-1-yl] -4-thiazolcarboxamide.

G) Growth regulators

- abscisic acid, amidochlor, ancimidol, 6-benzylaminopurine, brassinolide, butraline, clormequat (clormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipine, 2,6-dimethylpuridine, ethephon, flumetralol, flurprimidol, flurprimidol flurprimide , gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthalenacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmone, thidiazurone, thiazthioaturone, thiazthioaturone, of tributyl, 2,3,5-triiodobenzoic acid, trinexapaco-ethyl and uniconazole;

H) Herbicides

-acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimetenamide, flufenaceto, mefenaceto, metolachlor, metazachlor, napropamide, naproanilide, petoxamide, pretylachlor, propachlor, tenylchloride;

-Amino acid derivatives: bilanaphos, glyphosate, glufosinate, sulfate;

-aryloxyphenoxypropionates: clodinafop, cihalofop-butyl, phenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;

-bipyridyls: diquat, paraquat;

- (uncle) carbamates: asulamo, butylate, carbetamide, desmedifamo, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, fenmedifamo, prosulfocarb, piributicarb, thiobencarb, trialate;

-cyclohexandionas: butroxidim, cletodim, cycloxidim, profoxidim, setoxidim, tepraloxidim, tralkoxidim;

-dinitroanilines: benfluralin, etalfluralin, orizaline, pendimethalin, prodiamine, trifluralin;

- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyphene, fomesaphene, lactophen, oxyfluorfen;

-hydroxybenzonitriles: bomoxynil, diclobenyl, ioxynil;

-imidazolinones: imazametabenz, imazamox, imazapic, imazapiro, imazaquin, imazetapiro;

Phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, mecoprop;

-pyrazines: chloridazone, flufenpyr-ethyl, flutiacete, norflurazone, pyridate;

-pyridines: aminopiralid, clopiralid, diflufenican, dithiopor, fluridone, fluroxipir, picloramo, picolinafeno, thiazopor;

sulphonylureas: amidosulfuron, azimsulfuron, bensulfuron, clorimurona-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfurona, flupirsulfurona, foramsulfurona, halosulfuron, imazosulfuron, yodosulfurona, mesosulfurona, metazosulfurona, metsulfurona-methyl, nicosulfuron, oxasulfurona, primisulfuron, prosulfuron , pyrazulfulfone, rimsulfurone, sulfometurone, sulfosulfurone, tifensulfurone, triasulfurone, tribenurone, trifloxisulfurone, triflusulfurone, tritosulfurone, 1 - ((2-chloro-6-propylimidazo [1,2-b] pyridazin-3-yl) sulfonyl) , 6-dimethoxypyrimidin-2-yl) urea;

-triazines: ametrine, atrazine, cyanazine, dimethamethrin, ethiozine, hexazinone, methamitron, metribuzine, promethrin, simazine, terbutylazine, terbutrine, triaziflamus;

-ureas: chlorotolurone, daimurone, diurone, fluometurone, isoproturone, linurone, metabenzthiazurone, tebutiurone;

-other acetolactate synthase inhibitors: bispiribaco-sodium, chlorarandamo-methyl, diclosulamo, florasulamo, flucarbazone, flumetsulamo, metosulamo, ortho-sulfamurone, penoxsulamo, propoxycarbazone, pyribambenz-propyl, pyribenzoimyl, pyrinotalbyrio, pyrinotalbodiopyrimino, pyrinotalbodiopyrimino, pyrinotalbodiopyrimino, pyrinotalimino, pyrinotalbodio, pyrinotalimino, pyrinotalbodio, pyrinotalbodio, pyrinotalimodiopyrimino, pyrinotalimodiol poroxasulfone, poroxsulamo;

-Other: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone, benfluresato, benzofenap, bentazone, benzobicyclon, biciclopirona, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-etlilo, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide Dicamba diphenzoquat

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diflufenzopiro, monoceras Drechslera, endothal, ethofumesate, etobenzanid, fenoxasulfona, fentrazamide, flumicloracpentilo, flumioxazin, flupoxamo, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methylarsonic acid, naptalamo, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacilo, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, ethyl ester (3- [2-chloro- 4-fluoro-5- (3-methyl-2,6-dioxo-4-trifluoromethyl-3,6dihydro-2H-pyrimidin-1-yl) phenoxy] pyridin-2-yloxy) acetic acid, 6-amino acid methyl ester -5-Chloro-2-cyclopropylpyrimidin-4-carboxylic acid, 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazin-4-ol, 4-amino-3-chloro-6- (4-chlorophenyl) -5 -fluoropyridin2-carboxylic acid, 4-amino-3-chloro-6- (4-chloro-2-fluoro-) methyl ester 3-Methoxyphenyl) pyridin-2-carboxylic acid, and 4-amino-3-chloro-6- (4-chloro-3-dimethylamino-2-fluorophenyl) pyridine-2-carboxylic acid methyl ester.

I) Insecticides

-organo (uncle) phosphates: acephate, azamethylphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorphenvinphos, diazinone, dichlorvos, dichrotophos, dimethoate, disulfotone, ethion, fenitrothione, phentione, isoxationa, malationa methiona, methampionate , monocrotophos, oxidemethylmethyl, paraoxone, parathion, fentoate, fosalone, fosmet, phosphamidone, forate, foxime, pyrimiphos-methyl, prophenophos, protiophos, sulprophos, tetrachlovinphos, terbuphos, triazophos, trichlorfone;

-carbamates: alanicarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, phenoxycarb, furatiocarb, methiocarb, methtyl, oxamyl, pyrimicarb, propoxur, thiodicarb, triazamate;

Pyrethroids: aletrin, biphentrine, ciflutrin, cyhalotrine, kyphrenotrine, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, sphevalerate, etofenprox, fenpropatrin, fenvatrinatrine, imvaletrine, pervaletrine, pervaletrine, pervaletrine, ivaprinetrine, pervaletrine, ivaprinetrine, ivaprinetrine, ivaprinetrine, ivane resmethrin, silafluophen, tau-fluvalinate, teflutrin, tetramethrin, tralometrine, transflutrin, proflutrin, dimeflutrin;

- Insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazurone, ciramazine, diflubenzurone, flucycloxurone, flufenoxurone, hexaflumurone, lufenurone, novalurone, teflubenzurone, triflumurone; buprofezin, diophenolane, hexithiazox, ethoxazole, clofentazine; b) ecdisone antagonists: halofenozide, methoxyphenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyphene, methoprene, phenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifene, spirotetramate;

-Nicotinic receptor agonist / antagonist compounds: clothianidine, dinotefuran, imidacloprid, thiamethoxamo, nitenpyram, acetamipride, thiaclopride, 1- (2-chlorothiazol-5-ylmethyl) -2-nitrimino-3,5-dimethyl- [1,3, 5] triazinan;

-GABA antagonist compounds: endosulfan, ethiprole, fipronyl, vanyliprol, pyrafluprol, pyriprole, 5-amino-1- (2,6-dichloro-4-methylphenyl) -4-sulfinamoyl-1H-pyrazol-3-carbothioic acid amide ;

macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoramo;

- mitochondrial electron transport inhibitor acaricides (METI) I: phenazaquine, pyridabeno, tebufenpirad, tolfenpirad, flufenerimo;

- METI II and III compounds: acequinocil, fluaciprimo, hydramethylnone;

-couplers: chlorphenapiro;

-inhibitors of oxidative phosphorylation: cyhexatin, diafentiurone, fenbutatin oxide, propargite;

-compounds that alter the molt: cryomazine;

- mixed oxidase function inhibitors: piperonyl butoxide;

- sodium channel blockers: indoxacarb, metaflumizona;

-other: benclothiaz, bifenazate, cartap, flonicamide, pyridalyl, pimetrozine, sulfur, thiocyclalamus, flubendiamide, chlorantraniliprole, ciazipiro (HGW86), cenopyrphene, flupirazophos, ciflumetofen, amidoflumethin, pyriflucinate, pyriflucinate, pyriflutronaceum, pyriflumethione, pyriflucinate, pyriflucinate, pyrifluoromene, pyriflucinate, pyrifluoromethane, pyrifluoromene, pyriflucinate

In a preferred embodiment, the pesticide has a water solubility of less than 10 g / l at 20 ° C, more preferably less than 1 g / l, even more preferably less than 0.5 g / l, and most preferably less than 0, 1 g / l

Examples of suitable pesticide active ingredients, for the purposes of the present invention,

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they include, but are not limited to atrazine, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (commonly referred to under the trade name Diuron®), carbaryl, tebuconazole, chlorothalonyl, copper oxychloride, carbendazim, and metolachlor. The most preferred pesticides are diphenoconazole, metrafenone, and a mixture of diphenoconazole and metrafenone. The total amount of active substance or substances present in the composition is generally up to 60% in

5 weight, as an alternative of 10% to 50% by weight, as an alternative of 20% to 50% by weight, based on the total weight of the composition. In this regard, the composition may include relatively high amounts of the active substance or substances, compared to formulations intended for use by the end user.

The composition also includes a polymeric additive. The benefits associated with the polymeric additive are generally pronounced in compositions that have high amounts of the substance or substances.

10 active; however, the benefits associated with the polymeric additive also appear in compositions that have low amounts of the active substance or substances. The polymeric additive has at least one unit represented by the formula (I):

image2

wherein each R is independently selected from the group of a hydrogen atom, an alkyl group, an aryl group, and combinations thereof; and Z comprises at least 10 units represented by formula (II):

image3

wherein each R1 is independently selected from the group of a hydrogen atom, an alkyl group, an aryl group, a carbonyl group, a hydroxyl group, an ether group, and combinations thereof; and R2 is a C1-C10 hydrocarbon group. It should be noted that, when present, the alkyl and / or aryl groups of R and / or R1

20 can be monovalent.

Preferably, each R is independently selected from the group of a hydrogen atom, a C1 to C5 alkyl group, and combinations thereof. More preferably, each R is independently selected from the group of a hydrogen atom, a methyl group, and combinations thereof. It is especially preferred that R is a hydrogen atom.

Preferably, R1 is independently selected from the group of a hydrogen atom, an alkyl group, and combinations thereof. More preferably, R1 is a hydrogen atom. R2 is preferably a C1-C5 hydrocarbon group. R2 is more preferably a methyl group.

In a preferred embodiment, R is independently selected from the group of a hydrogen atom, a C1 to C5 alkyl group, and combinations thereof, R1 is a hydrogen atom, and R2 is a methyl group.

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Generally, the number of units represented by formula (II) that may be present in Z is from 10 to 200, as an alternative of 20 to 100, as an alternative of 30 to 70, and as an alternative of 40 to 60 units. Generally, the unit represented by formula (II) is present in an amount of 45% to 75% by weight, and alternatively 55% to 65% by weight, based on the total weight of the polymeric additive.

In one embodiment, Z further comprises at least one unit represented by formula (IV):

image4

wherein each R3 is independently selected from the group of a hydrogen atom, an alkyl group, an aryl group, a carbonyl group, a hydroxyl group, an ether group, and combinations thereof; and in which R3 is not an ester group. When present, the number of units represented by formula (IV) that may be present in Z is 10 to 200, as an alternative of 20 to 100, and as an alternative of 30 to 70. It is contemplated that the units represented by the formula (II), and when present by formula (IV), may be distributed randomly or in block form within Z. Preferably, Z comprises up to 20 molar units of formula (VI), more preferably up to 5% molar, and especially up to 0.5% molar.

Generally, the number of units represented by the formula (I) that are present in the polymeric additive is from 1 to 30, as an alternative from 1 to 15, and as an alternative from 3 to 10 units represented by the formula (I).

When the polymeric additive has at least two units represented by formula (I), the polymeric additive can be called a "comb" polymer due to its structure. It is contemplated that when the polymeric additive has at least two units represented by formula (I), each unit may be distributed randomly or regularly along the polyether skeleton.

The polymeric additive further includes at least one unit represented by the formula (III):

image5

wherein A is an alkyleneoxy group having 2 to 10 carbon atoms, preferably 2 to 5, and especially 2 to 3 carbon atoms. A can independently represent the same alkyleneoxy group or different alkyleneoxy groups having 2 to 10 carbon atoms. Examples of suitable alkyleneoxy groups include, but are not limited to ethylene oxide, propylene oxide, butylene oxide, decene oxide and styrene oxide. It is contemplated that when A represents different alkyleneoxy groups, the different alkyleneoxy groups may be distributed randomly or in block form within the polyether skeleton. In one embodiment, A represents the same alkyleneoxy group and A is ethylene oxide. When present, the number of units represented by formula (III) that may be present in the polymeric additive is from 10 to 150, and alternatively from 25 to 80.

The number of units represented by the formula (I), and when present by the formula (III), substantially control the length of the chain in the polymeric additive. In addition, the number of units represented by formula (I) and formula (III), as well as the number of units present in Z and the number of units represented by formula (IV), substantially control the number average molecular weight of the polymeric additive. In one embodiment, the polymeric additive has a molecular weight Pn of 5,000 to 200,000 g / mol, and alternatively 15,000 to 50,000 g / mol. The polymeric additive may be terminated with hydroxy groups or be alkylated into one or both terminal OH groups. Suitable alkyl radicals are branched or unbranched C1 to C22 radicals. Preferably, the polymeric additive is terminated with hydroxy groups.

In a preferred embodiment, the polymeric additive comprises:

1) at least one unit represented by the formula (I), in which each R is independently selected from the group of a hydrogen atom, an alkyl group, and combinations thereof: and Z comprises at least 10 units represented by the formula ( II), in which each R1 is a hydrogen atom; and R2 is a C1-C5 hydrocarbon group; Y

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2) at least one unit represented by formula (III), in which A is an alkyleneoxy group having 2 to 3 carbon atoms.

In a more preferred embodiment, the polymeric additive comprises:

1) at least one unit represented by formula (I), wherein each R is a hydrogen atom; and Z comprises at least 10 units represented by formula (II), wherein each R1 is a hydrogen atom; and R2 is a methyl; Y

2) at least one unit represented by formula (III), in which A is an alkyleneoxy group having 2 carbon atoms.

The polymeric additive can be obtained by well known methods for graft polymerization. An advantageous procedure is indicated, for example, in WO 2007/138053, page 5, line 14 to page 10, line 25.

The polymeric additive is generally present in the composition in an amount of at least 0.5% by weight based on the total weight of the composition. Alternatively, the polymeric additive is present in the composition in an amount of 0.5% to 10.0%, as an alternative of 0.5% to 5%, and as an alternative of 1% to 3% by weight, based on The total weight of the composition. In another preferred embodiment, the amount of the polymeric additive is usually in the range of 5% to 1000% by weight, preferably 10% to 500% by weight, more preferably 20% to 100% by weight, based on weight. of the active substance.

Although no limitation is intended by the theory, it is believed that the polymeric additive increases the performance and / or increases the stability of the active substance included in the composition depending on the specific active substance or substances included in the composition. More specifically, it is believed that the polymeric additive increases the stability of the active substance by wrapping around the active substance. As discussed in more detail below, the polymeric additive is particularly effective in stabilizing any active substance or substances capable of being transported through a continuous aqueous phase to thereby produce Ostwald maturation.

The composition may also comprise additional components other than the active substance and the polymeric additive. For example, the composition may include wetting agents; surfactants; emulsifiers; antifreeze to improve the freeze / thaw stability of the composition; defoamers; anti-deposit agents, such as xanthan gum; biocides; and combinations of the additives mentioned above. However, it should be appreciated that wetting agents, surfactants and emulsifiers are optional. Examples of suitable wetting agents include those selected from the group of alkoxylated alcohols, polyalkylene glycol ethers, naphthaleneformaldehyde sulphonate condensates, and combinations thereof. Examples of an alkoxylated alcohol include, but are not limited to Lutensol® XL and Lutensol® XP, commercially available products from BASF Corporation. An example of a polyalkylene glycol ether includes, but is not limited to Pluriol® WSB 125, commercially available from BASF Corporation. An example of a naphthaleneformaldehyde sulphonate condensate is Morwet® D425, commercially available from AkzoNobel. Although Morwet® D425 is a known additive, it can also be included for its known wetting properties. In the context of the present invention, Morwet® D425 can be included primarily as a wetting agent. In one embodiment in which the composition further comprises the wetting agent, the wetting agent may be presented in an amount of 1% to 20% by weight, based on the total weight of the composition. Alternatively, the wetting agent may be present in an amount of 1% to 10%, more generally 1% to 5%, and most generally 2% to 4%, based on the total weight of the composition. Examples of suitable surfactants may include anionic surfactants, such as calcium dodecylbenzenesulfonate. Examples of suitable emulsifiers may include non-ionic emulsifiers, such as alkoxylated alcohols, as described above. Generally, additional components are present in an amount of up to 20% by weight, and more generally up to 15% by weight, based on the total weight of the composition.

The active substance can also be diluted with a solvent component to form the composition. The solvent component may include water, water miscible liquids, oils, oil miscible liquids, propylene glycol, tripropylene glycol, acetaldehyde, other known vehicles, and combinations thereof. In one embodiment, more water and water-miscible constituents are present than oils and oil-miscible constituents. Under these circumstances, the solvent component may comprise a continuous aqueous phase. When included, the solvent component is generally present in the composition in an amount of 10% to 75% by weight, as an alternative of 10% to 60% by weight, as an alternative of 20% to 50% by weight, as an alternative to 30% to 40% by weight, based on the total weight of the composition.

In a preferred embodiment, the active substance is a pesticide and the composition according to the invention is an agrochemical composition. These agrochemical compositions may also comprise agents.

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auxiliaries that are common in agrochemical compositions. The auxiliary agents used depend on the specific application form and the active substance, respectively. Examples of suitable auxiliary agents are solvents, solid carriers, dispersants or emulsifiers (such as other solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, antifreeze agents, or antifoaming agents.

Suitable solvents for agrochemical compositions are water, organic solvents, such as medium to high boiling mineral oil fractions, such as kerosene or diesel oil, and also coal tar oils and oils of vegetable or animal origin. , aliphatic, cyclic and aromatic hydrocarbons, for example, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols, such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones, such as cyclohexanone and gammabutyrolactone, of fatty acids, fatty acids and fatty acid esters, and very polar solvents, for example, amines, such as N-methylpyrrolidone. In a preferred embodiment, the solvent comprises water. The water content of the agrochemicals composition is preferably at least 10% by weight, more preferably at least 25% by weight, and most preferably at least 35% by weight, based on the total weight of the composition. The composition may comprise up to 80% by weight of water.

Suitable surfactants for agrochemical compositions (adjuvants, humectants, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsulfonic acid (Borresperse®, Borregard, Norway types ), phenolsulfonic acid, naphthalene sulfonic acid (types Morwet®, Akzo Nobel, USA), dibutylnaphthalenesulfonic acid (types Nekal®, BASF, Germany), and fatty acids, alkylsulfonates, alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates, alcohol sulfates fatty, and hexa-, sulfated hepta- and octadecanoates, glycol ethers of sulfated fatty alcohol, and in addition condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, isooctylphenol ethoxylated, octylphenol, nonylphenol, alkylphenyl ether, polyphenyl ether, ethylphenyl ether , triestearylphenyl polyglycol ether, alkylaryl polyether alcohols, c alcohol and fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, residual liquors and lignin sulphite proteins, denatured proteins, polysaccharides (for example, methylcellulose), hydrophobically modified starches, polyvinyl alcohols (types Mowiol®, Clariant, Switzerland), polycarboxylates (types Sokolan®, BASF, Germany), polyalkoxylates, polyvinylamine (types Lupasol®, BASF, Germany), polyvinylpyrrolidone and their copolymers .

Examples of thickeners for agrochemical compositions (i.e., compounds that impart a modified fluidity to the compositions, that is, a high viscosity under static conditions and a low viscosity during stirring) are organic and anorganic polysaccharides and clays, such as gum. of xanthan (Kelzan®, CP Kelco, USA), Rhodopol® 23 (Rhodia, France), Veegum® (RT Vanderbilt, USA) or Attaclay® (Engelhard Corp., NJ, USA). Bactericides can be added for agrochemical compositions for the preservation and stabilization of the composition. Examples of suitable bactericides are those based on dichlorophen and benzyl hemi formal alcohol (Proxel® from ICI or Acticide® RS from Thor Chemie, and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazolinones (Thor Chemie Acticide® MBS). Examples of suitable antifreeze agents for agrochemical compositions are ethylene glycol, propylene glycol, urea and glycerin. Examples of antifoaming agents for agrochemical compositions with silicone emulsions (such as, for example, Silikon® SRE, Wacker, Germany, or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, fatty acid salts, fluoroorganic compounds and mixtures thereof.

The agrochemical composition, which comprises a pesticide as an active substance, may be present in any type of formulation known for agrochemical compositions, for example, solutions, emulsions, suspensions, fine powders, powders, pastes and granules. Preferably, the agrochemical composition is a suspension. The type of formulation depends on the specific intended objective; in each case, it must ensure a fine and uniform distribution of the compound according to the invention.

Examples of types of formulations are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, tablets, wettable powders or fine powders (WP, SP, SS, WS, DP , DS) or granules (GR, FG, GG, MG), which can be water soluble or wettable, as well as gel formulations for the treatment of plant propagation materials, such as seeds (GF). Typically, the types of formulations (for example, SC, OD, FS, EC, WG, SG, WP, SP, SS, WS, GF) are used diluted. The types of compositions such as DP, DS, GR, FG, GG and MG are usually used undiluted. Preferred types of formulations are suspensions, for example, SC.

The agrochemical compositions in general comprise between 0.01% and 95%, preferably between 0.1% and 90%, most preferably between 0.5% and 90% by weight of pesticide. Pesticides are used with a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

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In a preferred embodiment, the agrochemical composition is a dispersion (eg, emulsion or suspension, or suspoemulsion), preferably a suspension. More preferably, the agrochemical composition is an aqueous dispersion, such as an aqueous suspension. The pesticide may be present in any form, such as solid, liquid or dissolved. Preferably, the pesticide is present in solid form, more preferably in the form of solid particles, which are suspended in the composition. The average particle size of the suspended pesticide is generally at least 40% less than 2.0 µm, preferably at least 55%, as determined by dynamic light scattering.

The viscosity of a liquid agrochemical composition is usually up to 1000 mPas, preferably up to 700 mPas, more preferably up to 500 mPas, and especially up to 400 mPas (measured according to the requirements of the Food and Agriculture Organization (FAO) MT 192).

In a preferred embodiment, the composition according to the invention comprises metrafenone, diphenoconazole, and a polymeric additive comprising:

1) at least one unit represented by the formula (I), in which each R is independently selected from the group of a hydrogen atom, an alkyl group, and combinations thereof: and Z comprises at least 10 units represented by the formula ( II), in which each R1 is a hydrogen atom; and R2 is a C1-C5 hydrocarbon group; Y

2) at least one unit represented by formula (III), in which A is an alkyleneoxy group having 2 to 3 carbon atoms.

In another preferred embodiment, the composition according to the invention is a dispersion (for example, emulsion or suspension, or suspoemulsion), comprising a pesticide, and a polymeric additive comprising:

1) at least one unit represented by the formula (I), in which each R is independently selected from the group of a hydrogen atom, an alkyl group, and combinations thereof: and Z comprises at least 10 units represented by the formula ( II), in which each R1 is a hydrogen atom; and R2 is a C1-C5 hydrocarbon group; Y

2) at least one unit represented by formula (III), in which A is an alkyleneoxy group having 2 to 3 carbon atoms.

The present invention also relates to the use of the composition according to the invention, in which the active substance is a pesticide, to enhance the pesticidal activity of said pesticide. Preferably, the amount of the polymeric additive is in the range of 10% to 500% by weight, based on the weight of the pesticide.

The present invention also relates to a use of the composition according to the invention, in which the active substance is a pesticide, to enhance the retention of said pesticide on plants.

Ostwald maturation

In one embodiment, the active substance is in the form of solid particles and is capable of being transported through a continuous aqueous phase, when present, to thereby produce Ostwald maturation. The active substance that is capable of Ostwald maturation is referred to herein as the "M.O. In a specific embodiment, the composition includes the substance M.O., a solvent component comprising a continuous aqueous phase to dilute the substance M.O., and the polymeric additive. This particular embodiment of the composition is referred to herein as a "suspension composition" and will be described in more detail below. It should be appreciated that oils and oil miscible components may also be present, in which case the composition can be referred to, from a technical point of view, as a suspoemulsion. However, to simplify, a "suspension composition" refers to suspensions and suspoemulsions.

As discussed above, the substance M.O. it can include any substance that is capable of being transported through a continuous aqueous phase, to thereby produce an Ostwald maturation of the substance M.O. in the suspension composition. Ostwald maturation is a spontaneous process that is conducted thermodynamically, in which the particles dispersed in a fluid change in size over time. Specifically, larger particles are more energetically favored than smaller particles. As a result, the surface molecules detach from the smallest particles, are generally transported through the fluid by diffusion, and are incorporated into the larger particles. As larger particles increase their size further over time, the incidence of particles deposited outside the fluid also increases. Ostwald maturation can be easily observed by measuring differences in particle size over time for a specific suspension composition. For the purposes of the present application, a substance that is capable of Ostwald maturation shows an increase in the average particle size of the substance of at least 0.1 micrometers

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after preservation of a suspension composition at a temperature of 40 ° C for a period of 28 days, or after a few freeze-thaw cycles of the suspension composition for 7 days at temperatures ranging from -15 ° C to + 5 ° C. It should be noted that higher temperatures may increase the appearance of Ostwald ripening.

Generally, the substance M.O. in the suspension composition it has a degree of solubility in the continuous aqueous phase. However, if the solubility of the substance M.O. in the continuous aqueous phase the molecules of the substance M.O. are too high. they will travel through the continuous aqueous phase too quickly. As a result, the maturation of Ostwald can be so great that it is not possible to control it, and the substance M.O. it can be deposited outside the continuous aqueous phase, even when the polymeric additive is included in the suspension composition. Therefore, the substance M.O. It is generally partially water soluble and has a low solubility in the continuous aqueous phase of up to 500 ppm, generally 10 to 100 ppm at temperatures of -15 ° C to 54 ° C. In some cases, the solubility of the substance M.O. in the continuous aqueous phase it is 100 ppm to 500 ppm. As described in more detail below, a particular advantage of the suspension composition of the present invention is the ability to employ M.O. which are soluble in the continuous aqueous phase in excess of 100 ppm, with a limited maturation of Ostwald over time, compared to previously known suspension compositions.

The substance M.O. It is generally present in the suspension composition in the form of particles having an average particle size in weighted volume of 1.5 to 3.2 micrometers, alternatively 1.5 to 2.8 micrometers, as measured by an analyzer of the size of Mastersizer 2000® particle. The substance M.O. generates grinds to an average particle size in a weighted volume of 1.5 to 2.2 micrometers. Generally, the substance M.O. It has a distribution of the average particle size in weighted volume that is monomodal. The term "monomodal" refers to a collection of particles that have a unique and clearly discernible maximum in the particle size distribution curve (volume percentage on the Y axis, and particle size on the X axis). For the purposes of the suspension composition described herein, the "single maximum and clearly discernible" is generally located in the particle size distribution curve of 1.5 to 3.2 microns. In addition, approximately 90% of the particles of the M.O. they are generally below a particle size of 3.8 micrometers. In addition, the substance M.O. It generally has no particles that have a particle size greater than 10 micrometers. It should be noted that, due to the fact that the substance M.O. it has a degree of solubility in the continuous aqueous phase, at least a part of the substance M.O. It can be dissolved in the suspension composition.

In addition, the substance M.O. It is generally present in the suspension composition that includes the aqueous phase in an amount of up to 60% by weight, as an alternative of 30% to 55% by weight, as an alternative of 40% to 50% by weight, based on the total weight of the suspension composition. In this regard, the suspension composition generally includes relatively high amounts of the M.O. substance, compared to formulations that are intended for use by the end user. For example, when the substance M.O. it is a pesticide component that comprises an active pesticide ingredient, the suspension composition having the substance M.O. present in the above amounts may be a suspension concentrate that is diluted with more water to form agrochemical compositions with a water base that are then applied by the end user to the plants. As discussed above, the suspension composition also comprises a polymeric additive, as described above. Due to the high amount of M.O. which is generally included in the suspension composition, and due to the relatively hydro-insoluble nature of the M.O. substance, the polymeric additive is included in the suspension composition in order to stabilize the M.O. within the continuous aqueous phase of the suspension composition. The polymeric additive is generally included in suspension compositions that have high amounts of the substance M.O .; however, the polymeric additive is also effective for stabilization of suspension compositions that have low amounts of the substance M.O. The polymeric additive acts as well as the industry model additives, as determined by suspensibility tests, which are described in detail below. The polymeric additive that is included in the suspension composition of the present invention also inhibits or limits Ostwald maturation of the substance M.O. within the suspension composition, as described in more detail below, and this inhibition of Ostwald ripening is more effective than the performance of industry model additives in some circumstances.

The polymeric additive is present in the suspension composition in an amount sufficient to limit Ostwald maturation of the substance M.O. in the suspension composition. For the purposes of the present application, Ostwald maturation of the substance M.O. is “limited” when the change in the average particle size of the substance M.O. it is less than 1.2 micrometers after keeping the suspension composition at a temperature of 40 ° C for a period of 28 days, or after a freeze-thaw cycle of the suspension composition for 7 days at temperatures varying from -15 ºC to +5 ºC. Generally, the polymeric additive is present in an amount of at least 0.5% by weight, based on the total weight of all components present in the suspension composition, which is an amount sufficient to limit ripening.

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of Ostwald of the substance M.O. in the suspension composition. Alternatively, the polymeric additive is present in the suspension composition in an amount of 0.5% to 10.00%, as an alternative of 0.5% to 5.0%, and as an alternative of 1.0% to 3 , 0% by weight, based on the total weight of the suspension composition. It should be appreciated that the polymeric additive described herein provides suspensibility properties sufficiently acceptable to the suspension composition, and sufficiently prevents the maturation of Ostwald, so that the additional anti-deposition agents (described above as additional components that may be present) are not necessary in many cases. However, depending on the specific active substance that is included in the suspension composition, the anti-deposition agent may be included in the suspension compositions to further stabilize the suspension composition.

In a specific embodiment, the suspension composition includes a solvent component comprising a continuous aqueous phase in an amount of 10.0% to 60.0% by weight, the substance M.O. in an amount of up to 60.0% by weight, the polymeric additive in an amount of at least 0.5%, a wetting agent in an amount of 1.0% to 20.0%, and additional components in an amount of up to 20.0% by weight, all based on the total weight of the suspension composition.

In another specific embodiment, the suspension composition includes a solvent component comprising a continuous aqueous phase in an amount of 30% to 40% by weight, the substance M.O. in an amount of 40% to 50% by weight, the polymeric additive in an amount of 1% to 3%, a wetting agent in an amount of 2% to 4%, and additional components in an amount of up to 15% by weight , all based on the total weight of the suspension composition.

In another specific embodiment, the suspension composition includes a solvent component comprising a continuous aqueous phase and an oil in an amount of 18% to 72% by weight, the substance M.O. in an amount of 5% to 30% by weight, a second active substance that is liposoluble in an amount of 5% to 30% by weight, the polymeric additive in an amount of 1% to 5% by weight, a wetting agent in an amount of 1% to 5%, an emulsifier in an amount of 3% to 7% by weight, and additional components in an amount of up to 20% by weight, all based on the total weight of the suspension composition.

In another specific embodiment, the suspension composition includes a solvent component comprising a continuous aqueous phase and an oil in an amount of 18% to 72% by weight, the substance M.O. in an amount of 15% to 25% by weight, a second active substance that is liposoluble in an amount of 15% to 25% by weight, the polymeric additive in an amount of 2% to 4% by weight, a wetting agent in an amount of 2% to 3%, an emulsifier in an amount of 4% to 6% by weight, and additional components in an amount of up to 15% by weight, all based on the total weight of the suspension composition.

As described above, if the specific polymeric additive is included in the suspension composition, there is less maturation of Ostwald over time with the substance M.O. in the suspension composition, compared to when other additives are used. Although no limitation is desired by any particular theory, it is believed that the polyether skeleton allows the polymeric additive to be wrapped around the molecules and / or particles of the active substance, thus producing a lower Ostwald maturation of the active substance at the long of the time. In addition, this action with respect to the inhibition of Ostwald maturation allows the active substances to have a greater solubility in water than is currently accepted in the suspension composition. In particular, the change in the average particle size of the substance M.O. it is generally less than 2.0 and more generally less than 1.2 micrometers after keeping the suspension composition at a temperature of 40 ° C for a period of 28 days or after a freeze-thaw cycle of the suspension composition for 7 days at temperatures ranging from 15 ° C to +5 ° C.

Procedure to prepare the composition

A process for preparing a composition according to the present invention comprises the step of combining the active substance and the polymeric additive in a container to form the composition. In one reaction, the combination step may also comprise combining the solvent component in the container to form the composition. In another embodiment, the combination step may also comprise the step of combining a grinding medium with at least one of the active substance and / or the polymeric additive in the container to form the composition. Crushing means are known in the art. In another embodiment, the combination step may also comprise the step of combining the wetting agent with at least one of the active substance and / or the polymeric additive in the container to form the composition. Alternatively, the combination step may also comprise the step of combining the crushing medium and the wetting agent with at least one of the active substance and / or the polymeric additive in the container to form the composition. The container is generally a chamber of spheres of an Eiger mill; however, the container may, alternatively, be a mixing vessel of an Attritor mill, such as the Union Process Attritor system. The process may also comprise the step of decreasing the size of the active substance, generally by grinding, to a size

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particle average in weighted volume of 1.5 to 2.0 micrometers. The step of decreasing the size of the active substance generally occurs after combining the active substance and the polymeric additive to form the composition. The composition is generally cooled during milling to prevent the active substance from decomposing or melting during milling.

To test the composition to prevent the onset of Ostwald ripening, the composition can be stored at a temperature of 40 ° C for a period of 28 days, or the composition can be subjected to freeze-thaw cycles for 7 days at temperatures that they vary from -15 ° C to +5 ° C, and under these conditions the change in the average particle size of the active substance may be less than 1.2 micrometers after storage or the freeze-thaw cycles of the composition under certain circumstances, which represents a better performance in relation to the maturation of Ostwald of the active substance present in the composition, compared to the performance of model additives.

The advantages of the present invention are, for example, that the composition has excellent stability (for example, with respect to particle size, viscosity). The composition increases the pesticidal activity of the pesticide. This adjuvant effect is achieved without a decrease in the stability of the composition. The polymeric additive has a very low phytotoxicity, which is especially important for the treatment of vegetables and fruits. The polymeric additive can be easily produced on an industrial scale to reduce the cost. The polymeric additive increases the retention of pesticides on the leaves (spray retention).

The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention in any way.

Examples

Preparation of polymeric additive A

Polyethylene glycol (0.44 kg, Pn 6000) was melted at 90 ° C and 0.6 g of tert-butyl per-2-ethylhexanoate, dissolved in tripropylene glycol, was added. 7.75 mol of vinyl acetate were added with stirring in the next 6 h (feed 1), as well as 7 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in tripropylene glycol, in the next 6.5 h (feed 2), and also starting 3 h after starting feed 1, 0.23 kg of an alkoxylated C10 alcohol (feed 3) was dosed in a parallel and continuous manner with constant flow rates at a temperature of 90 ° C. At the end of feeds 2 and 3 and subsequent stirring at 90 ° C for one more hour, 6 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in tripropylene glycol, was added in 3 portions at 90 ° C with subsequent stirring for two hours in each case. A solids content of approximately 88% by weight was established by adding water. The resulting grafted polymer (polymer additive A) has a K value of 17-19 (1% by weight of polymer in aqueous sodium chloride (3% by weight) at 23 ° C), Pm 36,000, and Pn 20,000 (measured by a gel permeation chromatography, PMMA standard).

Preparation of the compositions (part I)

Compositions were prepared that include the components indicated in the following table 1, and all the amounts listed are presented in percentage by weight based on the total weight of the respective composition.

Table 1A - Composition of the examples according to the invention

Component

Ex. 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6

Constituent solvent A

34.55 34.55 34.65 34.45 34.45 34.45

Constituent solvent B

10.0 10.0 10.0 10.0 10.0 10.0

Constituent solvent C

0.045 0.045 0.045 0.045 0.045 0.045

Wetting agent A

3.5 3.5 3.5 3.5 3.5 3.5

Wetting agent B

0.225 0.225 0.225 0.225 0.225 0.225

Polymeric additive A

1.08 1.08 1.08 1.08 1.08 1.08

Active substance 1

50.0 50.0 50.0 - - -

Active substance 2

- - - 50.0 50.0 50.0

Additional component A

0.5 0.5 0.5 0.5 0.5 0.5

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Additional component B

0.1 0.1 - 0.2 0.2 0.2

Total

100.0 100.0 100.0 100.0 100.0 100.0

Component

Ex 7 Ex 8 Ex 9 Ex 10 Ex 11

Constituent solvent A

34.4 34.38 39.4 34.65 39.4

Constituent solvent B

10.0 10.0 10.0 10.0 10.0

Constituent solvent C

0.045 0.045 0.045 0.045 0.045

Wetting agent A

- - 3.5 3.5 3.5

Wetting agent B

0.225 0.225 0.225 0.225 0.225

Polymeric additive A

1.08 1.08 1.08 1.08 1.08

Polymeric additive D

3.5 3.5 - - -

Active substance 2

50.0 50.0 - - -

Active substance 3

- - 45.0 50.0 45.0

Additional component A

0.5 0.5 0.5 0.5 0.5

Additional component B

0.25 0.27 0.25 - 0.25

Total

100.0 100.0 100.0 100.0 100.0

Table 1B - Composition of comparative examples (not according to the invention)

Component

Eg comp. one Eg comp. 2 Eg comp. 3 Eg comp. 4 Eg comp. 5 Eg comp. 6

Constituent solvent A

34.5 34.5 34.5 34.3 34.25 34.5

Constituent solvent B

10.0 10.0 10.0 10.0 10.0 10.0

Wetting agent A

3.5 3.5 3.5 3.5 3.5 3.5

B polymeric additive

1.5 1.5 1.5 1.5 1.5 1.5

Active substance 1

50.0 50.0 50.0 - - -

Active substance 2

- - - 50.0 50.0 -

Active substance 3

- - - - - 50.0

Additional component A

0.5 0.5 0.5 0.5 0.5 0.5

Additional component B

- 0.2 0.25 -

Total

100.0 100.0 100.0 100.0 100.0 100.0

Component

Eg comp. 7 Eg comp. 8 Eg comp. 9 Eg comp. 10 Eg comp. eleven Eg comp. 12

Constituent solvent A

34.5 34.5 39.25 34.5 34.5 34.4

Constituent solvent B

10.0 10.0 10.0 10.0 10.0 10.0

Wetting agent A

3.5 3.5 3.5 - - -

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B polymeric additive

1.5 1.5 1.5 - - -

C polymeric additive

- - - 2.0 2.0 2.5

Polymeric additive D

- - - 3.0 3.0 3.5

Active substance 1

- - - 50.0 50.0 50.0

Active substance 3

50.0 50.0 45.0 - - -

Additional component A

0.5 0.5 0.5 0.5 0.5 0.5

Additional component B

- - 0.25 - - 0.1

Total

100.0 100.0 100.0 100.0 100.0 100.0

Component

Eg comp. 13 Eg comp. 14 Eg comp. fifteen Eg comp. 16 Eg comp. 17 Eg comp. 18

Constituent solvent A

34.4 34.5 34.3 34.3 34.3 34.5

Constituent solvent B

10.0 10.0 10.0 10.0 10.0 10.0

C polymeric additive

1.5 1.5 1.5 1.5 1.5 1.5

Polymeric additive D

3.5 3.5 3.5 3.5 3.5 3.5

Active substance 1

50.0 50.0 - - - -

Active substance 2

- - 50.0 50.0 50.0 -

Active substance 3

- - - - - 50.0

Additional component A

0.5 0.5 0.5 0.5 0.5 0.5

Additional component B

0.1 - 0.2 0.2 0.2 -

Total

100.0 100.0 100.0 100.0 100.0 100.0

Component

Eg comp. 19 Eg comp. twenty Eg comp. twenty-one

Constituent solvent A

34.5 39.3 39.3

Constituent solvent B

10.0 10.0 10.0

C polymeric additive

1.5 1.5 1.5

Polymeric additive D1)

3.5 3.5 3.5

Active substance 3

50.0 45.0 45.0

Additional component A

0.5 0.5 0.5

Additional component B

- 0.2 0.2

Total

100.00 100.00 100.00

-The solvent constituent A is water.

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-The solvent constituent B is 1,2-propylene glycol.

-The solvent constituent C is tripropylene glycol containing trace amounts of acetaldehyde.

-The wetting agent A is Pluriol® WSB 125 from BASF Corp., a polyalkylene glycol ether.

-The wetting agent B is Lutensol® XL 100 from BASF SE, an ethoxylated C10-Guerbet alcohol, the degree of ethoxylation is equal to approximately 10.

-Polymeric additive A was prepared as described above.

-The polymeric additive B is Atlox® 4913 from Uniquema, a comb polymer based on methyl methacrylate, methacrylic acid and methoxypolyethylene glycol methacrylate.

- Polymeric additive C is a difunctional block copolymer surfactant that terminates in primary hydroxyl groups, commercially available from BASF Corporation.

-The polymeric additive D is Morwet® D425 from Akzo Nobel, a sodium salt of an alkylnaphthalene sulfonate condensate.

-The active substance 1 is atrazine (a herbicide).

-The active substance 2 is 3- (3,4-dichlorophenyl) -1,1-dimethylurea (a herbicide, also known as DCMC).

-The active substance 3 is carbaryl (an insecticide).

-Additional component A is an antifoaming agent.

-Additional component B is an anti-deposit agent.

The compositions will be prepared by first weighing the appropriate amount of the solvent constituent A to be used to prepare the compositions and adding the solvent constituent A to a container. The appropriate amounts of the polymeric additive and the wetting agent are then determined according to the values indicated in Table 1 and added to the container. The contents of the container are then mixed until the polymeric additive and the wetting agent are dispersed in the solvent constituent A.

The active substance is then added to the container, followed by mixing until the contents of the container appear uniform. Then the additional components, the solvent constituent B and the solvent constituent C are added to the container, the container is covered, and the contents of the container are mixed for 1 hour.

An Eiger Mini 50 ball mill is then used which comprises a ball chamber to grind the contents of the container to form the composition. The sphere chamber is cooled using a refrigerant system with a refrigerant comprising a 50/50 parts by volume water / propylene glycol mixture. To grind the contents of the container, a zirconium grinding medium having an average diameter of 0.8 to 1.0 mm, in an amount of 80 ml, is included in the sphere chamber. The cooling system is then used to cool the chamber of spheres to a temperature of 5 ° C to 10 ° C. Then a spindle mill bypass valve for recirculation is adjusted. The contents of the container are then added to the sphere chamber and grinding is started with the sphere mill in the recirculation mode, taking care to ensure that the temperature of the contents in the sphere chamber is not greater than 40 ºC. Samples are periodically extracted from the ball mill to measure the particle size, until a particle size in weighted volume of the samples between 1.7 to 2.0 micrometers is achieved, without particles larger than 10 micrometers. Obtaining the desired particle size indicates obtaining the composition, and the contents of the chamber of spheres (excluding spheres) are collected for the assay.

Stability test after freezing / defrosting

For the test, the compositions of the present invention are subjected to freeze / thaw and storage cycles for high temperature conditions as follows: The freeze-thaw cycles of the composition are performed by repeated temperature cycles of a sample test of the composition from -15 ºC to +5 ºC. Each freeze-thaw cycle has a duration of one week and includes 3.5 days of storage at -15 ° C, followed by 3.5 days of storage at +5 ° C. After completing a minimum of 6 freeze / thaw cycles, the physical properties of the sample are evaluated and compared with the initial measurements to determine the effects that may adversely alter the useful handling and end-use properties of the sample. composition.

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Conservation test under high temperature conditions

Conservation was carried out under high temperature conditions by placing a sample of the composition in an oven maintained at a surrounding air temperature of 40 ° C or 54 ° C, depending on the substance included in the composition, for a period of 28 days, after which the physical properties of the sample are evaluated and compared with the initial measurements to determine the effects that may adversely alter the useful handling and final use properties of the composition. It was found that compositions including carbaryl form pastes after storage at 54 ° C. Conservation under these conditions of elevated temperatures for compositions including carbaryl is carried out by placing a sample of the composition in an oven maintained at a surrounding air temperature of 40 ° C for a period of 28 days, after which the physical properties of the sample and are compared with the initial measurements to determine the effects that may adversely alter the useful handling and end-use properties of the composition containing carbaryl.

Measurement of particle size in the compositions

The physical properties of the compositions are measured according to the following procedures, the physical properties being measured initially after the preparation of the compositions, after the freeze / thaw cycles, and after storage under elevated temperature conditions as described above. .

Samples of the composition are dispersed in deionized water and analyzed for particle size by placing a Malvern Mastersizer 2000 particle size analyzer, commercially available from Malvern Instruments, Southborough, MA. The sample is dispersed using a small volume recirculator and the operations are performed using a conventional operating procedure (SOP) specifically created to include sample parameters such as refractory index, mixing speed, analysis time, and number of measurements . The analysis is based on spherical assumptions and the results are indicated in terms of average diameter in weighted volume (ie, average particle size in weighted volume). The results are based on an acquisition interval of 0.02-2000 µm and on the average of two trials.

The initial particle sizes for each of the examples and comparative examples, as described above, are indicated in the following table 3. The particle sizes for each of the examples and comparative examples, as described above. , are indicated in the following table 3, after subjecting the examples and comparative examples to a freeze / thaw cycles, as described above. The change in particle size after the freeze / thaw cycles is indicative that Ostwald maturation occurs within the respective compositions.

Table 3 - Results of freeze / thaw cycles (particle size is indicated as average particle size in weighted volume)

Component

Initial particle size [µm] Final particle size [µm] Change in particle size,%

Example 1

2,119 2,152 1,560

Example 2

2,030 2,062 1,580

Example 3

1,734 2,051 18,280

Example 4

1,634 1,544 -5,510

Example 5

2,037 2,034 -0,150

Example 6

1,818 1,770 -2,640

Example 7

1,686 not rehearsed not rehearsed

Example 8

1,689 not rehearsed not rehearsed

Example 9

1,716 1,730 0.820

Example 10

2,057 2,211 7,490

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Example 11

1,864 1,824 -2,150

Comparative Example 1

1,600 1,619 1,190

Comparative Example 2

1,640 1,626 -0,850

Comparative Example 3

1,700 1,676 -1,410

Comparative Example 4

1,450 1,574 8,550

Comparative Example 5

1,483 3,334 124,810

Comparative Example 6

2,077 2,030 -2,260

Comparative Example 7

2,054 2,120 3,210

Comparative Example 8

1,974 2,230 12,970

Comparative Example 9

2,095 2,127 1,530

Comparative Example 10

1,450 1,415 -2,410

Comparative Example 11

1,483 1,458 -1,690

Comparative Example 12

2,077 2,097 0.960

Comparative Example 13

2,054 2,069 0.730

Comparative Example 14

1,974 2,048 3,750

Comparative Example 15

1,301 1,331 2,310

Comparative Example 16

1,689 2,133 26,290

Comparative Example 17 *

1,883 1,779 -5.52

Comparative Example 18

1,518 42,100 2673,390

Comparative Example 19

1,455 43,520 2891,070

Comparative Example 20

1,661 1,675 0.840

Comparative Example 21

1,631 2,110 29,370

* Comparative example 17 was evaluated after 30 freeze / thaw cycles.

The statistical analysis for the increase in particle size after the freeze / thaw cycles was performed using JMP 8 software. The results of the statistical analyzes indicate that the differences in the average particle size in weighted volume between the examples and the

5 comparative examples are not statistically significant, thereby indicating that the polymeric additives used in the examples are as effective as the additives used in the comparative examples.

The particle size for each of the examples and comparative examples, as described above, is indicated in the following table 4, after subjecting the examples and comparative examples to preservation under high temperature conditions, as described above. . The change in

Particle size after preservation under high temperature conditions is also indicative that Ostwald maturation occurs within the respective compositions.

Table 4 -Reservation results at an elevated temperature (particle size is indicated as average particle size in weighted volume)

Component

Initial particle size [µm] Final particle size [µm] Change in particle size,%

Example 1

2,119 2,364 11,560

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Example 2

2,030 2,390 17,730

Example 3

1,734 2,350 35,520

Example 4

1,634 2,068 26,560

Example 5

2,037 2,601 27,690

Example 6

1,818 2,340 28,710

Example 7

1,686 2,260 34,050

Example 8

1,689 2,247 33,040

Example 9 **

1,716 N / A N / A

Example 10 **

2,057 N / A N / A

Example 11

1,864 3,015 61,750

Comparative Example 1

1,600 1,741 8,810

Comparative Example 2

1,640 1,798 9,630

Comparative Example 3

1,700 1,873 10,180

Comparative Example 4

1,450 3,081 112,480

Comparative Example 5

1,483 3,340 125,220

Comparative Example 6 **

2,077 N / A N / A

Comparative Example 7 **

2,054 N / A N / A

Comparative Example 8 **

1,974 N / A N / A

Comparative Example 9

2,095 2,570 22,670

Comparative Example 10

1,450 1,757 21,170

Comparative Example 11

1,483 1,788 20,570

Comparative Example 12

2,077 2,327 12,040

Comparative Example 13

2,054 2,282 11,100

Comparative Example 14

1,974 2,331 18,090

Comparative Example 15

1,301 1,765 35,660

Comparative Example 16

1,689 2,133 26,290

Comparative Example 17

1,883 2,241 19,010

Comparative Example 18 **

1,518 N / A N / A

Comparative Example 19 **

1,455 N / A N / A

Comparative Example 20

1,661 2,505 50,810

Comparative Example 21

1,631 104,470 6305,270

** The data is not available since the example formed a paste.

Statistical analysis for the increase in particle size after storage under high temperature conditions was performed using JMP 8 software. The results of the statistical analyzes indicate

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that the differences in the average particle size in weighted volume between examples 1-11 and comparative examples 1-21 are not statistically significant when the active substance used is atrazine, thereby indicating that the polymeric additives used in these examples are so effective as the additives used in the respective comparative examples. When the active substance used is 3- (3,4-dichlorophenyl) 1,1-dimethylurea, the results indicate that although examples 1-11 have a smaller change in an average particle size than comparative examples 1-21, the difference in average particle size in weighted volume between examples 1-11 and comparative examples 1-21 is not statistically significant, which indicates that the polymeric additives used in these examples are as effective as the additives used in the respective examples comparatives When the active substance used is carbaryl and a thickener is present, the results indicate that the differences in the average particle size in weighted volume between examples 1-11 and comparative examples 1-21 are not statistically significant, indicating that The polymeric additives used in these examples are as effective as the additives used in the respective comparative examples. However, when the active substance used is carbaryl and a thickener is not present, differences in average particle size in weighted volume between examples 1-11 and comparative examples 18 and 19 indicate that a statistically significant minimization of Ostwald maturation when the polymeric additives of the examples are used, instead of the additives in comparative examples 18 and 19.

Suspensibility test

To test the suspensibility of the compositions, 150 ml of conventional hard water (containing hard water ions, such as magnesium and calcium, are measured in an amount of 342 ppm with a molar ratio of calcium ions to magnesium ions of 2: 1 ) in a 250 ml beaker. A magnetic stirrer is placed in the beaker and this is placed on a stir plate. The speed of the stir plate is adjusted so that the vortex does not reach the stir bar.

Then 5.00 ± 0.10 grams of the composition is weighed on a weighing tray and placed in the beaker. A stopwatch is immediately started and adjusted for 2 minutes, also adjusting the agitator speed after adding the sample of the composition to the beaker to ensure a good mixing.

After 2 minutes of mixing, the beaker is removed from the stir plate. The magnetic stirrer is removed and rinsed using a wash bottle filled with conventional hard water. The contents of the beaker are then poured into a 250 ml graduated cylinder and the beaker is rinsed with the rinse added to the 250 ml graduated cylinder. The volume in the cylinder is brought to 250 ml using conventional hard water. The stages of emptying and rinsing the beaker are performed in 1 minute.

The 250 ml graduated cylinder is then sealed and inverted for 15 cycles at 2-3 seconds per cycle and then allowed to stand at room temperature for 30 minutes.

Then 225 ml of the suspension is extracted from the 250 ml graduated cylinder in 10-25 seconds using a pipette and always keeping the tip of the pipette only a few mm below the surface of the liquid in the 250 ml graduated cylinder , being careful to minimize the disturbance of the entire cylinder. The liquid extracted using the pipette is discarded.

A dry evaporation plate is weighed to the nearest 0.05 grams. The remaining 25 ml in the 250 ml graduated cylinder are agitated to suspend the particles present inside, and the contents of the 250 ml graduated cylinder are poured into the evaporation plate. The 250 ml graduated cylinder is rinsed, the rinse being added to the evaporation plate.

The evaporation plate is then placed in a drying oven and allowed to dry overnight. When the contents of the evaporation plate are dry, it is removed from the oven and allowed to stand at an ambient temperature of 21 ° C for 5 minutes. Then the evaporation plate is weighed.

The suspensibility is then determined by subtracting the weight of the residue on the evaporation plate from the mass of solids in the initial sample of the composition, and then dividing the result by the weight of the residue on the evaporation plate (and multiplying by 100 to obtain a percentage). The suspensibility is determined initially, after storage at 40 ° C for 28 days, and after a few freeze / thaw cycles, and the results are shown in the following table 5.

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Table 5 - Results of the suspensibility test

Component

Initial Suspensibility,% Final susceptibility after storage at 40 ° C or 54 ° C for 28 days,% Final susceptibility after a few freeze / thaw cycles,%

Example 1

99.3 99.4 97.6

Example 2

102.9 102.2 98.6

Example 3

100.9 not rehearsed 100.6

Example 4

99.5 100.2 101.7

Example 5

105.4 97.2 98.8

Example 6

not rehearsed 100.1 99.7

Example 7

98.1 94.2 not rehearsed

Example 8

101.3 98.4 not rehearsed

Example 9

92.9 not rehearsed 100.1

Example 10

98.0 not rehearsed not rehearsed

Comparative Example 1

101.7 97.8 101.7

Comparative Example 2

101.0 N / A 99.3

Comparative Example 3

99.4 96.3 104.1

Comparative Example 4

91.9 89.4 92.6

Comparative Example 5

not rehearsed 95.2 98.4

Comparative Example 6

100.1 not rehearsed 98.9

Comparative Example 7

101.5 not rehearsed 101.1

Comparative Example 8

98.8 not rehearsed 101.0

Comparative Example 9

100.1 not rehearsed 99.3

Comparative Example 10

101.9 100.9 101.9

Comparative Example 11

100.1 98.4 98.6

Comparative Example 12

100.4 98.0 98.2

Comparative Example 13

101.0 97.6 97.6

Comparative Example 14

91.2 101.4 98.0

Comparative Example 15

98.9 101.4 100.5

Comparative Example 16

100.5 97.6 101.4

Comparative Example 17

99.2 98.9 106.2

Comparative Example 18

99.7 not rehearsed 100.9

Comparative Example 19

101.3 not rehearsed 96.3

Comparative Example 20

98.9 not rehearsed 100.9

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Comparative Example 21

not rehearsed not rehearsed 99.7

The results of the suspensibility tests for each of the examples and comparative examples, as described above, after freeze / thaw cycles and after storage under high temperature conditions, and differences in the suspensibility values between the

5 examples and comparative examples indicate that a statistically significant suspensibility is achieved when the polymeric additives of the examples are used, instead of the additives in the comparative examples.

Wet sieve analysis

A wet sieve analysis was performed according to a procedure described in the CIPAC manual in Wet Sieving MT 59.3. The initial test is carried out as soon as possible after preparing the compositions in the Eiger Mini mill

10 50. If the initial test is satisfactory, a sample that has undergone 6 weeks of freeze / thaw cycles is tested.

To perform the wet sieve analysis 7.62 cm sieves of 50, 100 and 325 mesh are used, and dried in an oven at 50 ° C overnight to prepare the test. The sieves are weighed individually.

25 gm of the composition are added to a 600 ml beaker, and the beaker is filled until

15 400 ml mark with tap water. The contents of the 600 ml beaker are then stirred with a magnetic stirrer for 5 minutes with a minimum vortex.

The stacked sieves are moistened with tap water and then the composition poured through the sieves. While still stacked, the sieves are rinsed with tap water to ensure that all the composition that can pass through the sieves does. The sieves are then dried in an oven at 50 ° C

20 overnight, and the sieves are weighed again.

The percentage of the composition retained in each sieve is calculated as follows:

Sieve weight plus residue - sieve weight = residue weight

% of the residue = weight of the residue / 25 * 100

The percentage of the composition retained on each sieve is indicated in the following table 6 (for the results

25 initials), table 7 (for results after storage under high temperature conditions of 40 ° C or 54 ° C for a period of 28 days), and table 8 (for results after freeze / thaw cycles).

Table 6 - Results of the wet sieving test

Component

Retention on a 50,% mesh wet sieve Retention on a 100% mesh wet sieve Retention on a 300 mesh wet sieve,%

Example 1

0.00 0.04 0.00

Example 2

0.00 0.00 0.00

Example 3

0.20 0.12 0.04

Example 4

0.04 0.00 0.04

Example 5

0.16 0.16 0.16

Example 6

0.07 0.00 0.00

Example 7

0.14 0.14 0.00

Example 8

0.28 0.14 0.00

Example 9

0.20 0.00 0.00

Example 10

0.12 0.04 0.08

Comparative Example 1

0.04 0.04 0.08

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Comparative Example 2

0.00 0.00 0.00

Comparative Example 3

0.00 0.00 0.04

Comparative Example 4

0.20 0.04 0.08

Comparative Example 5

0.04 0.04 0.04

Comparative Example 6

0.16 0.04 0.04

Comparative Example 7

0.04 0.16 0.00

Comparative Example 8

0.00 0.08 0.08

Comparative Example 9

0.04 0.04 0.04

Comparative Example 10

0.00 0.00 0.00

Comparative Example 11

0.08 0.08 0.00

Comparative Example 12

0.00 0.00 0.00

Comparative Example 13

0.04 0.00 0.00

Comparative Example 14

0.16 0.12 0.08

Comparative Example 15

0.06 0.00 0.11

Comparative Example 16

0.00 0.16 0.16

Comparative Example 17

0.08 0.00 0.04

Comparative Example 18

0.04 0.04 0.04

Comparative Example 19

0.12 0.00 0.00

Comparative Example 20

0.04 0.08 0.04

Table 7

Component

Retention on a 50,% mesh wet sieve Retention on a 100% mesh wet sieve Retention on a 300 mesh wet sieve,%

Example 1

0.00 0.00 0.04

Example 2

0.11 0.06 0.11

Example 4

0.00 0.00 0.00

Example 5

0.22 0.00 0.04

Example 6

0.11 0.05 0.00

Example 7

0.14 0.14 0.00

Example 8

0.28 0.14 0.00

Comparative Example 1

0.00 0.00 0.00

Comparative Example 3

0.00 0.00 0.00

Comparative Example 4

0.08 0.04 0.08

Comparative Example 10

0.04 0.00 0.00

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Comparative Example 11

0.04 0.00 0.00

Comparative Example 12

0.00 0.05 0.05

Comparative Example 13

0.04 0.00 0.04

Comparative Example 14

0.12 0.00 0.08

Comparative Example 15

0.13 0.00 0.04

Comparative Example 16

0.00 0.05 0.00

Comparative Example 17

0.20 0.12 0.00

Table 8

Component

Retention on a 50,% mesh wet sieve Retention on a 100% mesh wet sieve Retention on a 300 mesh wet sieve,%

Example 1

0.04 0.04 0.04

Example 2

0.09 0.00 0.00

Example 3

0.16 0.04 0.00

Example 4

0.04 0.00 0.00

Example 5

0.00 0.00 0.00

Example 6

0.05 0.00 0.00

Example 9

0.08 0.04 0.04

Example 10

0.20 0.32 0.08

Example 11

0.00 0.00 0.04

Comparative Example 1

0.16 0.08 0.08

Comparative Example 2

0.04 0.04 0.04

Comparative Example 3

0.04 0.04 0.08

Comparative Example 4

1.23 0.63 0.04

Comparative Example 5

0.00 0.00 0.00

Comparative Example 6

0.00 0.04 0.04

Comparative Example 7

0.04 0.04 0.16

Comparative Example 8

0.00 0.00 0.00

Comparative Example 9

0.12 0.08 0.00

Comparative Example 10

0.08 0.04 0.08

Comparative Example 11

0.04 0.04 0.08

Comparative Example 12

0.00 0.08 0.08

Comparative Example 13

0.00 0.00 0.00

Comparative Example 14

0.00 0.00 0.04

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Comparative Example 15

0.00 0.04 0.04

Comparative Example 16

0.00 0.00 0.00

Comparative Example 17

0.20 0.12 0.08

Comparative Example 18

0.04 0.00 0.00

Comparative Example 19

0.08 0.00 0.00

Comparative Example 20

0.04 0.04 0.00

Comparative Example 21

0.00 0.00 0.00

The results of the wet sieving tests for each of the examples and the comparative examples indicate that the compositions of the examples performed as well as the compositions of the comparative examples, retaining only insignificant amounts of the composition.

5 Preparation of the compositions (part II)

Table 9 lists the composition of example 22 and comparative examples 23 (without polymer additive) at 26. All data in table 9 is in g / l unless otherwise indicated. The compositions of examples 22 to 26 were prepared by mixing all the components and grinding them in a thermostated sphere mill until the desired particle size is reached.

10 Table 9 - Results of the pesticide activity potentiation test

Component

Ex 22 Ex. 232) Ex. 242) Ex. 252) Ex. 262)

Constituent solvent A

Up to 1.0 l Up to 1.0 l Up to 1.0 l Up to 1.0 l Up to 1.0 l

Constituent solvent B

70 70 70 70 70

Wetting agent C

30 30 30 30 30

Wetting agent D

twenty twenty twenty twenty twenty

Polymeric additive A

100 - - - -

Polymeric additive E1)

- - 100 - -

F1 polymeric additive)

- - - 100 -

Active substance 4

120 120 120 120 120

Active substance 5

300 300 300 300 300

Additional component A

5 5 5 5 5

Additional component C

2 2 2 2 2

Additional component D

2 2 2 2 2

Additional component E

- - - - fifteen

1) Polymeric additive for comparison, not according to the invention. 2) Comparative example.

-The wetting agent C is an EO / PO / EO block copolymer (molar mass of the PO block of about 3200 g / mol, about 50% by weight of PE in the molecule).

-The wetting agent D is a sodium salt of polymeric alkylnaphthalene sulfonate.

15-Polymeric additive E is a C9-C11 propoxylated ethoxylated alcohol (CAS # 103818-93-5), commercially available as Uniquema's Atplus® 245.

27

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-The polymeric additive F is an ethoxylated C13 alkyl alkoxylated alcohol. -The active substance 4 is diphenoconazole (a fungicide, water solubility of 3.3 mg / l at 20 ° C). -The active substance 5 is metrafenone (a fungicide, water solubility of 0.49 mg / l at 20 ° C). -The additional component C is an antibacterial agent.

5 -The additional component D is an xanthan gum.

-The additional component E is a C10 alkoxylated alcohol (the same as that used in the preparation of the above polymeric additive A). Test of particle size after storage The stability of the compositions was evaluated following the average particle size (percentage of particles with

10 a size <2 µm, as determined by dynamic light scattering), which was initially determined, and after a week of storage at 40 ° C or 50 ° C, respectively (see table 10). The stability of example 22 according to the invention was as good as the stability without the adjuvant (example 23). For comparison, a commercially available adjuvant, as in example 24, dramatically reduced the stability of the suspension, and the particle size increased greatly.

15 Table 10 - Particle size (percentage of particles with a size <2 µm) after storage

Composition

Initial (%) After one week at 40 ° C (%) After one week at 50 ° C (%)

Example 22

66 64 53

Comparative Ex. 23

66 63 59

Comparative Ex. 24

59 24 one

Comparative Ex. 25

65 29 4

Viscosity test after storage

The stability of the compositions was evaluated following the viscosity (analyzed) according to the requirements of the Food and Agriculture Organization (FAO) MT 192 (values in mPa · s), which was initially determined, and after a week of preservation at 40 ° C or 50 ° C, respectively (see table 11). The stability of example 22 according to the invention was as good as the stability without the adjuvant (example 23). For comparison, a commercially available adjuvant, as in example 24 and 25, dramatically reduced the stability of the suspension, and the viscosity increased greatly.

Table 11 - Viscosity after conservation

Composition

Initial (mPa · s) After one week at 40 ° C (mPa · s) After one week at 50 ° C (mPa · s)

Example 22

351 341 390

Comparative Ex. 23

28 27 28

Comparative Ex. 24

130 > 1000 > 1000

Comparative Ex. 25

221 > 1000 > 1000

25

Greenhouse pesticide activity test

Pesticide activity was tested in a greenhouse with grapes, which were infected with the oidium of the vine. The plants were treated with the composition of example 22 and example 23 at a dose ratio of 1.17, 4.69 or 18.75 ppm. The percentage of the disease was evaluated 21 and 28 days after infection (dpi). The test was performed twice and the results are summarized in Table 11 and 12. The data demonstrate that the composition of Example 22 (with adjuvant) has a higher pesticidal activity, compared to the composition of Example 23 without

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adjuvant

Table 11 - Pesticide activity (greenhouse)

Dose ratio (ppm)

Disease% 21 dpi Disease% 28 dpi

Untreated Control

- 17 39

Example 22

18.75 0.2 0

Example 22

4.69 2.5 0.6

Example 22

1.7 4.4 4

Comparative Ex. 23

18.75 0.1 0

Comparative Ex. 23

4.69 2.1 0.6

Comparative Ex. 23

1.17 eleven 14

Table 12 - Pesticide activity (greenhouse)

Dose ratio (ppm)

Disease% 21 dpi Disease% 28 dpi

Untreated Control

- 43 57

Example 22

18.75 0 0

Example 22

4.69 0.3 0.3

Example 22

1.7 0.8 4.6

Comparative Ex. 23

18.75 0 0.3

Comparative Ex. 23

4.69 0.1 0

Comparative Ex. 23

1.17 4 8.3

5

Testing of pesticide activity in a field

Pesticide activity was tested in a field with cucumbers, which were infected with the cucumber oidium. The plants were treated with the composition of example 22 and example 23 at a dose ratio of 1.17, 4.69 or 18.75 ppm. The percentage of the disease was evaluated on the upper and lower part of the leaves 6 days later

10 of the application (DDA). The tests were performed twice and the results are summarized in Table 13 (6 DDA) and 14 (8 DDA), and demonstrate that the composition of example 22 (with adjuvant) has a higher pesticidal activity, compared to the composition of the example 23 without adjuvant.

Table 13 - Pesticide activity (in the field)

Proportion of doses (g / ha)

% of disease, upper part of the leaves % of disease, lower part of the leaves

Untreated Control

- 53 63

Example 22

140 0.5 27

Example 22

105 0.3 14

Comparative Ex. 23

140 0.4 31

Comparative Ex. 23

105 0.4 26

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Table 14 - Pesticide activity (in the field)

Proportion of doses (g / ha)

% of disease, lower part of the leaves

Untreated Control

- 68

Example 22

140 5

Example 22

105 8

Comparative Ex. 23

140 fifteen

Comparative Ex. 23

105 2. 3

Comparative Ex. 24

140 7

Comparative Ex. 24

105 eleven

Comparative Ex. 25

140 6

Comparative Ex. 25

105 8

Comparative Ex. 26

140 14

Comparative Ex. 26

105 24

Test of the enhancement of retention of active substances on plants

A concentrate of an aqueous suspension containing fluxapiroxad 300 g / l, a dispersing agent, a

5 antifoam, a xanthan gum thickener, a bactericide, and a 1,2-propylene glycol antifreeze (called "White SC"). Polymeric additive A was optionally added. To measure the retention of an aqueous spray, the concentrated suspension was diluted with water and a fluorescent marker (fluorescein) to prepare a spray tank mixture. Said tank mixture was applied at a speed of 200 l / ha by means of a nozzle apparatus (type of nozzle: flat fan (air induction), DI 120.02, Lechler) at a

10 speed of 1.4 m / s with a pressure of 3.4 bar and a spray arm (1 m, 3 nozzles; distance of the nozzles 50 cm). The tank mixture was applied to wheat (var. Melon) in growth stage BBCH 12. After application the leaves of the plants were collected and washed with a defined amount of a wash solution (0.1 mol NaOH / l). The fluorescence intensity, which is proportional to the amount of active substance retained on the leaves, was measured with a fluorometer. Each experiment was repeated four times and the average of the values was

15 indicates in table 15. The data show that retention on plants increases due to polymeric additive A, compared to formulations without this additive or compared to water.

Table 15 - Plant Retention

Applied composition

Spray retention on the plant (fluorescence intensity per g of plant material and per ml of washing solution)

Water

1070

White SC1)

1228

SC white + 0.1% polymeric additive A 2)

1830

SC white + 0.2% polymeric additive A 2)

2459

1) Comparative, not according to the invention. 2) Concentration in the tank mixture.

Claims (15)

1. A composition comprising: an active substance; and a polymeric additive, which is obtained by graft polymerization, comprising: 1) at least one unit represented by the formula (I): image 1 wherein each R is independently selected from the group of a hydrogen atom, an alkyl group, an aryl group, and combinations thereof; and Z comprises at least 10 units represented by formula (II): image2 wherein each R1 is independently selected from the group of a hydrogen atom, an alkyl group, an aryl group, a carbonyl group, a hydroxyl group, an ether group, and their combinations; and R2 is a C1-C10 hydrocarbon group; Y 2) at least one unit represented by formula (III): image3 15 in which A is an alkyleneoxy group having 2 to 10 carbon atoms. 2. A composition according to claim 1, wherein said unit represented by formula (II) is present in said polymeric additive in an amount of 45% to 75% by weight, based on the total weight of said polymeric additive. 3. A composition according to claim 1 or 2, wherein said polymeric additive has an average numerical molecular weight of 5,000 to 200,000 g / mol. 4. A composition according to claims 1 to 3, wherein each R is independently selected from the group of a hydrogen atom, a methyl group, or combinations thereof, and A is an alkyleneoxy group having 2 31 at 3 carbon atoms. 5. A composition according to claims 1 to 4, wherein R1 is a hydrogen atom. 6. A composition according to claims 1 to 5, wherein R2 is a methyl group. 7. A composition according to claims 1 to 6, wherein said active substance is a pesticide. 8. A composition according to claim 7, wherein the pesticide is diphenoconazole, metrafenone, or a mixture of diphenoconazole and metrafenone. 9. A composition according to claim 7 or 8, wherein the composition is an aqueous suspension, and the pesticide is present in the form of solid particles, which are suspended in the composition. 10. A composition according to claims 1 to 9, wherein said polymeric additive is present in an amount of at least 0.5% by weight, based on the total weight of said composition. 11. A composition according to claims 1 to 10, wherein said polymeric additive is present in an amount of at least 5% by weight, based on the total weight of said composition. 12. A process for preparing a composition according to claims 1 to 11, comprising the step of combining the active substance and the polymeric additive to form the composition. 13. A method according to claim 12, further comprising the step of combining a grinding medium with at least one of the active substance and / or the polymeric additive when the active substance is in the form of solid particles. 14.-A procedure to control phytopathogenic fungi and / or unwanted plant growth and / or an unwanted attack of insects or mites and / or to regulate the growth of plants, in which the composition 20 is allowed according to Claims 1 to 11 act on the specific pest, its habitat or the plants to be protected against the specific pest, the earth and / or on unwanted plants and / or useful plants and / or their habitat. 15. A use of the composition according to claims 1 to 11, wherein the active substance is a pesticide, to enhance the pesticidal activity of said pesticide. 16. The use according to claim 15, wherein the amount of polymeric additive is in the range of 10% to 25,500% by weight, based on the weight of the pesticide. 17. A use of the composition according to claims 1 to 11, wherein the active substance is a pesticide, to enhance the retention of said pesticide on plants. 32